Process for dyeing synthetic fibers employing naphthyl dye assistants

ABSTRACT

Synthetic fibers are dyed with a disperse dyestuff and a carrier of the following formula:   WHEREIN Y is lower ester, ether or acyl and Z is lower alkyl, alkoxy or halogen. Preferred dye assistants include naphthyl carbonic acid esters.

United States Patent [191 Dellian et al.

[451 July 8,1975

[ PROCESS FOR DYEING SYNTHETIC FIBERS EMPLOYING NAPI-ITHYL DYEASSISTANTS [75] Inventors: Kurt A. Dellian, Ossining, N.Y.;

Samuel Lee, Fairlawn, NJ.

[73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Jan. 26, 1973 [21] Appl. No.: 326,921

FOREIGN PATENTS OR APPLICATIONS 1,139,108 l/l969 United Kingdom 700,75012/1964 Canada ..8/92

Primary ExaminerBenjamin R. Padgett Assistant Examiner-B. H. HuntAttorney, Agent, or F irmJoseph G. Kolodny; Edward McC. Roberts; Prabodhl. Almaula 5 7 ABSTRACT Synthetic fibers are dyed with a dispersedyestuff and a carrier of the following formula:

wherein Y is lower ester, ether or acyl and Z is lower alkyl, alkoxy orhalogen. Preferred dye assistants include naphthyl carbonic acid esters.

4 Claims, No Drawings PROCESS FOR DYEING SYNTHETIC FIBERS EMPLOYINGNAPHTHYL DYE ASSISTANTS BACKGROUND OF THE INVENTION The presentinvention is directed to a process for dyeing and/or printing ahydrophobic textile material, particularly polyesters or cellulosetriacetate. In particular, it relates to a dyeing process employing adyeing assistant which is substantially non-polluting and biodegradable.

Previously, in the dyeing or printing of textile fibers employing anorganic dyestuff of negligible watersolubility, it was necessary toemploy elevated pressures and temperatures beyond about 250F. Toovercome these costly and complex dyeing techniques, specific carriercomponents were added to the dyebaths. The carriers are compounds whichare capable of swelling the fibrous textile material or otherwiseaffecting the fiber and thus facilitating the penetration of thedyestuff into the fiber. Conventionally, the use of such carriers anddyebaths for hydrophobic fibers permits satisfactory dyeing attemperatures as low as 200-2l0F and permits the use of unpressurizedequipment.

Conventionally preferred dye carriers included chlorinated hydrocarbons,for example chlorinated benzene. Additionally other carriers, such asderivatives of benzene or phenol, such as orthoor paraphenylphenol,benzyl alcohol, benzene carbonic esters or ethers and benzoic orsalicylic acid have been employed.

While the performance of the prior art carriers has been generallysatisfactory with regard to assisting in dye penetration neverthelessthe carriers do possess numerous substantial undesirable ecologicalproperties. Such undesired properties included unacceptable toxicity,non-biodegradableness and undue odoriferousness. Apart from theecologically undesired side effects of the carriers, certain assistantsproduce variations in shade in the textile and also adversely effect thefastness of the dye.

Accordingly, it is a principal object of the present invention toprovide a process for dyeing hydrophobic fibers in the presence of anecologically acceptable dye carrier.

It is another object to the invention to provide a substantiallynon-polluting, low odor, low-toxic dye carrier which does not produceundesired variations in shade or dye fastness on a hydrophobic textilefiber.

The above and other objects are met in a process for coloring synthetichydrophobic fibers, or fabric with a dispersed dyestuff in a carrier ofthe following general formula:

wherein n=O to 2; a=l or 2; b=O to 2; Z is a radical which includes C C-alkyl, halogen and C C -alkoxy; Y is -COOR; -OR; OCOCH and OCOC H and Ris a radical which includes C C -alkyl, phenyl, benzyl and C C-cycloalkyl; wherein when n=0, Y is not -OR, said phenyl and benzylradicals each having from 0-2 Z groups substituted thereon.

The dye assistants of the present process have been found to be of lowodor, low toxicity and substantially biodegradable. From anenvironmental standpoint, these properties areextremely valuable. Inaddition to being ecologically desirable, the carriers also permit anefficient drawing rate for the dyestuff and aid in permitting goodfastness with uniform shade in the dyeing operation.

As employed herein, the term disperse dyestuff refers to organic coloredcompounds which are at most only slightly water-soluble. Conventionally,these disperse dyestuffs are applied in the form of aqueous dispersionswell known to those skilled in the art. The disperse dyestuffs employedare well known and may be the typical azo and amino anthraquinone dyes,as set forth in the Color Index (C.l.) for Disperse Dyes.

The hydrophobic textile materials that may be dyed according to thepresent process include fibers of polyamide, polyacrylate, modacrylatepolyester and preferably cationic modified polyester and cellulosetriacetate. Typical cationic modified polyester fibers are derived fromhigh melting linear polyethylene glycol terephthalate and include thefibers commercially available under the following trademarks: TERYLENE,DA- CRON, TERGAL, DIOLEN or TREVIRA. Typical commercially availablecellulose triacetate fibers include those identified by the marks ARNEL,TRICEL and COURPLETA. Blends and mixes of the aforesaid fibers may alsobe dyed employing the present ecologically desired dye assistants.

Typical dye carriers which are environmentally acceptable include:

O i ll I i\ o ca e 01 l) Description of Preferred Embodiments Formaximum effectiveness in the dyebath, the preferred carriers melt belowabout 100C. Further, the carriers and their substituents must besubstantially non-toxic, non-odoriferous and biodegradable. Accordingly,the preferred carriers employed in the dyeing process include naphthylcarbonic acid esters of the formula:

wherein R, is C C -alkyl, benzyl or phenyl; Z is halogen or C C -alkyl;n is O or 1 and b is O, l or 2. The particularly preferred halogensubstituent is chlorine.

The preferred R, groups have been found to be particularly ecologicallydesirable having substantially no odor and low toxicity in the carriercompounds.

In general, it is preferred that the lower alkyl and halogenconstituents on the naphthyl esters if present generally be limited to atotal of not more than one on each of the ring members.

Particularly preferred ecologically desirable carriers include a-methylnaphthoate; a-benzyl naphthoate; ,B-ethyl naphthoate; methly-a-naphthylacetate; oz-phenylnaphthoate and chlorophenyl-naphthyl acetate.

The benzyl and phenyl R and R groups may have substituted thereon up tothree C,C -alkyl and/or halogen groups. Preferably, if present at all, asingle halogen or lower alkyl group will be present on the phenyl orbenzyl ring.

It has been found that when other functional substituents are present onthe preferred naphthyl carbonic acid ester carriers, certain undesirableenvironmental problems can arise. For example, aldehyde or ketonesubstituents substituents tend to be undesirably odoriferous. Amidogroups generally raise the melting point of the carrier above about 100and render more difficult the aqueous dyeing process which is usuallyrun at atmospheric pressures.

In general, the carriers are dissolved, dispersed or emulsified in adyebath according to conventional procedures. It is preferred that thecarrier be emulsified, since the preferred ecologically desirablecarriers are water-insoluble. The carrier may be conventionallyemulsified by pre-mixing the carrier with the emulsifier and thereafterforming an emulsion in the dyebath. Alternatively, the carrier can bedissolved in a solvent, such as an alcohol, and then added to thedyebath which contains a suitable emulsifier. Examples of particularlyuseful emulsifiers include oxethylated sulfonates, alkylarylphenolsorsulfates of higher fatty acids. Other useful emulsifiersincludepolyglycol ethers derived from condensation of ethylene oxide and higherfatty alcohols, alkylphenols or fatty amines. Preferred emulsifiersinclude salts of sulfonated detergents as sulfonated benzimidazolessubstituted by higher alkyl radicals at the second carbon atom; salts ofmonocarboxylic acid esters of 4-sulfopl1thalic acid with higher fattyalcohols; salts of fatty alcohol sufonates, alkylaryl sulfonic acids orcondensation products of higher fatty acids with aliphatichydroxysulfonic or aminosulfonic acids.

Although the amountof emulsifier which may be employed may be widelyvaried, it is generally preferred for practicality and efficiency toemploy from about 3 to 20% of emulsifier based on the weight of carrier.Over 20% emulsifier by weight of carrier tend to be unduly excessive,while amounts under about 3% tend to be insufficient to bring theinsoluble carriers into a stable emulsion.

It is a significant feature of the invention that the preferred naphthylcarbonic acid ester carriers are stable both under acid and alkalineconditions and do not undergo decomposition during the dyeing orprinting process. These properties are in addition to theenvironmentally preferred properties of substantial nontoxicity,biodegradableness and non-odoriferous. Additionally, the esters do notundesirably influence the light fastness in dyeing processes ascontrasted with other conventional prior art carriers such asorthophenyl-phenol.

The naphthoic ether carriers of the present invention can be formed fromconventional procedures such as reacting an aor B-haloalkylenenaphthalene such as aor B-chloromethylnaphthalene with sodium ethoxide,thereby forming an ethyl alkylnaphthyl ether, such as ethylmethylenenaphthyl ether. The preferred naphthyl carbinol ester carrierscan be formed by reacting a suitable aor ,B-haloalkylnaphthalene such as0:- or B-chloroalkylnaphthalene with a potassium salt of a lowermolecular weight methyl carboxylic acid, such as acetic acid, to form anaphthyl carbinol ester, such as methyl-a-naphthyl acetate. To form theparticularly preferred naphthoic acid esters, an a,B-naphthoic acid maybe condensed according to conventional procedures with the desiredalcohol.

The concentration of the carrier in the dyebath may vary betweenrelatively broad ranges. It is preferable that from about 1 to 15%carrier by weight of textile goods (fabric) is employed. When theconcentration of the carrier rises above about 15%, a competing reactionoccurs which tends to strip the fiber simultaneously as the fiber isdyed. Below about 1% by weight, the carrier concentration isinsufficient to significantly penetrate and swell the fibrous materialto permit penetration of the dyestuff into the fiber.

Enhanced dyeing is obtained and consequently it is particularlypreferred that from about 2 to 8% by weight of carrier is employed basedon the weight of the textile goods. Of course, the particular optimumconcentration of carrier will depend in part on the type of disperse dyeemployed, the fiber to be dyed and the technique of application.

In general, the dyeing process may be employed with any of theconventional disperse dyestuffs known to the art. As illustrative ofsuitable disperse dyes are Color lndexC. l.Disperse Dyes. Typical azodisperse dyes are Cibacet Orange 2R (C.l. Disperse Orange 3) No. l 1005and Disperse Fast Yellow G (C.l. Disperse Yellow 3) No. 1 1855. Typicalanthraquinone dyes are exemplified by C1 Disperse Violet 8 No. 62030 andCl. Disperse Blue 1. Examples of other disperse dyes include C.l.Disperse Yellow 4; Disperse Yellow 1 No. 10345; Disperse Orange 13 No.20080; Disperse Orange 3 Nof 11005; Disperse Yellow 3 No. 11855;Disperse Orange l No. 11080; Disperse Red 19; Disperse Red 1 No. 1110;Disperse Red '131No. 11115; Disperse Red 11 No. 62015; Disperse Violet14; Disperse Blue 14 and Disperse Blue 24. Other suitable dyes includedispersible vat dyes such as C.I. Vat Red 41 No. 73300 and Cl. Vat Blue1 No. 73000.

The present treatment utilizing the naphthyl compounds as carriers isusually employed in atmospheric dyeing processes carried out attemperatures up to about the boiling point of water. If desired, thepresent process may be carried out as a pressurized dyeing pro-' cesswherein the dyebath is under a pressure of from about 3 to 4 atmospheresin a closed container at temperatures up to about 135C.

If desired, other well-known conventional constituents may be added tothe dyebath such as thickeners, anti-foaming agents, and the like. Otherconventional organic carriers may be admixed with thenaphthyl carriersin minor proportions. However, these carriers will reduce theecologically desirable properties of the present process to some degree.The present process is useful for both dyeing and printing applications.

In the following examples, the disperse dyes are brought into a state ofsuspension inthe dyebath employing conventional procedures. For example,the dye can be stirred with to times its weight of water at to C andallowed to stand for 10 minutes with occasional agitation. Before addingthe disperse jdyestuff to the dye liquor a conventional syntheticdispersing agent is put into the liquor to assist in maintaining astable suspension and increase the dispersability of the dye pigment inwater.

The following examples illustrate certain preferred embodiments of theinvention and are not limitative of scope.

EXAMPLE 1 as taught in Chemical Abstract, Vol. 74, Abstract No.10056(K)..

The liquid content of the dyebath was adjusted to provide a liquor tofabric weight ratio of 30: 1. Next a polyester fabric formed fromcationic modified polyethylene terephthalate was introduced into theaqueous dyebath.

The dyebath was raised to boiling and kept at the boil for 2 hours.Thereafter the fabric was rinsed and soaked. Next the fabric wassubjected to an aftertreatment bath containing 4 ml/l caustic soda, 38%Be and 5 g/l sodium hydrosulfite at C for 20 minutes. A deep red shadeof very good fastness was obtained. Similar results are obtainedemploying any of the following dye carriers'which are substituted forthe a-methylnaphthoate:

CH CH CH OCH v 2 2 2 3 Cn OCH Ch CH 7 i occn.

0 p HB c1 c1-I,.-ci1, .-c-0cH, Cl C0411 3,

L L J n A J I v CH2 ocn cii cn on c :11

EXAMPLE 2 An aqueous dyebath was formed containing 8% by weight of anemulsion consisting of 65% by weight of the total emulsion ofa-benzylnaphthoate by weight of the emulsion of the ammonium salt ofoxethylated nonylphenol sulfate by weight of the emulsion of water Adyestuff of the formula:

EXAMPLE 3 A polyester fabric was dyed in accordance with the procedureset forth in Example 1 with the exception that the dyestuff was replacedby an equal weight of:

OCH 0 NH O 3 A reddish blue shade of good all-round fastness wasobtained. 4O

EXAMPLE 4 A polyester fabric was dyed in accordance with the procedureset forth in Example 1 with the exception that an 8% emulsion containing70% by weight of the emulsion of B-ethylnaphthoate was employed. A deepred shade of very good fastness was obtained.

EXAMPLE 5 A polyethylene terephthalate fabric (polyester) was dyed inaccordance with the procedure set forth in Example l with the exceptionthat a mixture of 1% by weight of the dyestuff of Example 1 and Example2 were employed. An orange shade of generally good fastness wasobtained.

EXAMPLE 6 A polyethylene terephthalate fabric was dyed in accordancewith the procedure set forth in Example 2 with the exception that an 8%by weight of emulsion containing 65% by weight of the emulsion ofmethyl-anaphthyl acetate was employed. A deep yellow shade with goodall-round fastness was obtained.

EXAMPLE 7 A polyethylene terephthalate fabric was printed with a printpaste. The paste contained 20 g/k of the dyestuff employed in Example 1,5O g/k of a-phenylnaphthoate and a thickener of starch ether-locust beangum. The print was submitted to a 2-minute curing at 320F. A fast redshade was obtained.

EXAMPLE 8 A blend of polyethylene terephthalate (Dacron 54) fibers andanionic modified polyethylene terephthalate (Dacron 64) was dyed in anaqueous dyebath according to Example 1 with a liquor to fabric weightratio of 40:1. The bath contained 8 parts of an emulsion of parts ofchlorophenyl naphthylacetate and 15 parts of polyoxethylated phenolemulsifier. The aqueous dyebath also contained 1% of the dyestuffemployed in Example and 1% of the following dyestuff:

I L c 011 Cl. BASIC YELLOW B A uniform yellow shade was obtained withgood fastness properties.

It will be obvious to those skilled in the art that other carriers,dyestuffs and emulsifiers can be employed without departing from thespirit of the invention. Other modifications with regard to treatmentsteps, temperatures and other reaction parameters will be obvious tothose skilled in the art. While certain preferred embodiments aredisclosed herein, the invention is not to be limited except as set forthin the following claims:

Wherefore we claim:

1. A process for dyeing synthetic hydrophobic fibers or fabriccomprising treating said fibers with a mixture of a disperse dyestuffand a carrier which is a naphthyl carbonic acid ester of the formula (CH-COOR wherein R is C -C -alkyl, benzyl or phenyl; Z is halogen or C -C-alkyl; n is 0 or 1 and b is 0, l or 2; and said benzyl and phenyl eachhave from 0-2 Z radicals substituted thereon.

2. A process for dyeing polyester fibers or fabric in a dyebath whichcomprises a mixture of a disperse dyestuff and a carrier of the formulaI jiij (CH COOR wherein R is C -C alkyl, benzyl or phenyl; Z is halogenor C -C -alkyl; n is O or 1 and b is 0, 1 or 2.

3. The process of claim 2 wherein the carrier is added to the dyebath inthe form of an emulsion which comprises the carrier, from 15-20% byweight of carrier of an emulsifier and water.

4. The process in accordance with claim 2 wherein the dyebath containsfrom about 1-15% by weight of carrier based on the weight of the fabricto be dyed.

1. A process for dyeing synthetic hydrophobic fibers or fabriccomprising treating said fibers with a mixture of a disperse dyestuffand a carrier which is a naphthyl carbonic acid ester of the formula 2.A PROCESS FOR DEYING POLYESTER FABRICS IN A DYEBATH WHICH COMPRISES AMIXTURE OF A DISPERSE DYESTUFF AND A CARRIER OF THE FORMULA
 3. THEPROCESS OF CLAIM 2 WHEREIN THE CARRIER IS ADDED TO THE DYEBATH IN THEFORM OF AN EMULSION WHICH COMPRISES THE CARRIER, FROM 3-20% BY WEIGHT OFCARRIER OF AN EMULSIFER AND WATER.
 4. The process in accordance withclaim 2 whereIn the dyebath contains from about 1-15% by weight ofcarrier based on the weight of the fabric to be dyed.